EP1012199B1 - Struktur-klebstoffe auf polyurethan basis - Google Patents

Struktur-klebstoffe auf polyurethan basis Download PDF

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Publication number
EP1012199B1
EP1012199B1 EP98946442A EP98946442A EP1012199B1 EP 1012199 B1 EP1012199 B1 EP 1012199B1 EP 98946442 A EP98946442 A EP 98946442A EP 98946442 A EP98946442 A EP 98946442A EP 1012199 B1 EP1012199 B1 EP 1012199B1
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EP
European Patent Office
Prior art keywords
range
functionality
polyol
component
structural adhesive
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Expired - Lifetime
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EP98946442A
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English (en)
French (fr)
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EP1012199A1 (de
Inventor
Eric-Jack Gerard
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Kraton Polymers Research BV
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Kraton Polymers Research BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property

Definitions

  • the present invention relates to a structural adhesive comprising a polyurethane, and to a multi-component system, in particular a two-component system for preparing such structural adhesive.
  • the present invention further relates to articles containing the structural adhesive.
  • thermoset reaction products of polyols with aromatic polyisocyanates compounded with tackifying resins and plasticizers can be used for high-temperature-resistant masking tapes.
  • European patent application publication No. 0 709 416 describes pressure sensitive adhesives and laminating adhesives which contain thermoset polyurethanes.
  • the polyurethane is prepared from a polyisocyanate having a functionality of from 2.2 to 10 and a mixture of a hydrogenated polydiene mono-ol and a hydrogenated polydiene diol.
  • the polyurethane is prepared from a hydrogenated polydiene diol and a polyisocyanate having a functionality of from 2.2 to 10, wherein the NCO:OH molar ratio is between 0.3:1 and 0.7:1.
  • EP-A-0 293 602 and corresponding US 4,820,368 describe a thermally stable reactive hot melt urethane adhesive composition having a thermoplastic polymer, a compatible curing urethane polyalkylene polyol pre-polymer and a tackifying agent.
  • the polyalkylene polyol is preferably a hydrogenated polybutadiene diol, either having a 1,2 vinyl content ("b" in the formula on page 4 of EP-A-0 293 602) before hydrogenation of 0 to 20 % by weight, or 80 to 100 % by weight.
  • the NCO:OH ratio in the urethane pre-polymer is well above 2 in all examples.
  • EP-A-0 504 436 describes a two-part polyurethane adhesive.
  • the polyurethane preferably has a NCO:OH ratio of 2 to 10.
  • the two component system consists of a main component comprising a hydroxyl-terminated saturated polyester resin or a polyester urethane rubber and a curing agent comprising a urethane pre-polymer having an active isocyanate group which is prepared by reacting a hydrogenated hydroxyl terminated polybutadiene with an excess amount of a polyisocyanate.
  • the hydroxyl-terminated polybutadiene can have 0-100 % of 1,2 vinyl content. In the Examples a hydroxyl-terminated polybutadiene is used, having a 1,2 vinyl content prior to hydrogenation of about 20% by weight.
  • EP-A-0 522 658 describes functionalised block copolymers cured with isocyanates, for example for use in coatings.
  • the functionalised block copolymers are typically functionalised, hydrogenated styrene-butadiene-styrene block copolymers.
  • a hydroxy functional hydrogenated polybutadiene having a 1,2 vinyl content prior to hydrogenation of 84% by weight, is reacted with triisocyanates at a NCO:OH ratio of 1.25 and 1.5 and formed into a coating.
  • polyurethane-based structural adhesives have now been found which solve one or more problems encountered with known structural adhesives.
  • polyurethane-based structural adhesives have been found which have better tack and cohesive properties, can adhere to a variety of substrates including polyolefins and can be used up to high temperatures.
  • the present invention relates to a structural adhesive composition
  • a polyurethane which is obtainable by reacting a polyisocyanate having a functionality in the range of from 2 to 3 and a hydrogenated polybutadiene polyol, having a functionality in the range from 1.5 to 2.5, and a 1,2 vinyl content prior to hydrogenation of from 30 to 70% by weight, and wherein the NCO:OH molar ratio is in the range from more than 1.05 up to 1.6.
  • the functionality of the polyol is less than 1.5, the cohesive properties of the structural adhesive are too low. If the functionality of the polyol is more than 2.5, the structural adhesive may be too highly crosslinked and lack rubbery behaviour.
  • the functionality is defined as the number of functional groups, that is hydroxy groups, per molecule.
  • the functionality F can be determined by NMR or chemical titration techniques.
  • the functionality of the polyol ranges from 1.7 to 2.4.
  • the desired flexibility and cohesion of the structural adhesive can be influenced by selecting a functionality for the polyol within the above ranges.
  • the hydrogenated polybutadiene polyol has a 1,2-addition between 30% and 70% to minimise viscosity and subsequent crystallisation. More preferably, the 1,2 vinyl content in the hydrogenated polybutadiene polyol is between 40% and 60%.
  • the polybutadiene diol used in this invention may be prepared anionically such as described in United States patent specification Nos. 5,376,745, 5,391,663, 5,393,843, 5,405,911, and 5,416,168.
  • the anionic polymerisation of butadiene in a hydrocarbon solvent like cyclohexane is typically controlled with structure modifiers such as diethylether or glyme (1,2-diethoxy-ethane) to obtain the desired amount of 1,2-addition.
  • structure modifiers such as diethylether or glyme (1,2-diethoxy-ethane) to obtain the desired amount of 1,2-addition.
  • the optimum balance between low viscosity and high solubility in a hydrogenated polybutadiene polymer occurs at a 60/40 ratio of 1,4-butadiene / 1,2-butadiene.
  • This butadiene microstructure may e.g. be achieved during polymerisation at 50°C in cyclohexane containing about 6% by volume of diethylether or about 1000 ppm of glyme.
  • the polybutadiene diol can also be made using a mono-lithium initiator which contains a hydroxyl group which has been blocked as the silyl ether (as in United States patent specification Nos. 5,376,745 and 5,416,168).
  • a suitable initiator is hydroxypropyllithium in which the hydroxyl group is blocked as the trimethylsilyl ether.
  • This mono-lithium initiator can be used to polymerise butadiene in hydrocarbon or polar solvent.
  • Each mole of living polymer is then capped with one mole of ethylene oxide and terminated with one mole of methanol to yield the mono-hydroxy polydiene polymer.
  • the silyl ether is then removed by acid catalysed cleavage in the presence of water yielding the desired polybutadiene diol.
  • the polybutadiene diols preferably have hydroxyl equivalent weights in the range of from 250 to 10,000, more preferably in the range of from 500 to 7,500.
  • the polyurethane composition can be formed by curing into a mould for several hours and then postcuring the product for a period of time at elevated temperature, typically for 0.5 to 24 hours at a temperature of at least 50 °C, preferably at a temperature in the range from 60 °C to 150 °C, for example above 110°C for at least 2 hours or at 80 °C for 7 hours.
  • the polyurethane composition is formed by mixing the polyisocyanate and the polyol and curing the mixture at ambient temperature.
  • the mixture can be cured outdoors. Due to the small excess of isocyanate, water additionally reacts with the isocyanate to form amines which crosslink with other isocyanate groups to form additional crosslinks (postcuring).
  • the structural adhesive of the present invention may optionally comprise a tackifying resin.
  • Tackifying (tackifier) resins are known to those skilled in the art and have for example been described in detail in the Handbook of Pressure Sensitive Adhesive Technology, 2 nd ed., 1989, edited by Donatas Satas, pages 527 to 544.
  • the tackifying resin is selected from aliphatic oligomers derived from C 2 -C 10 aliphatic mono-ene or diene monomers, preferably derived from C 4 -C 6 aliphatic monomers, rosin esters, hydrogenated rosins, poly (terpene) resins, alpha-pinene resins, beta-pinene resins, hydrocarbon resins of petroleum origin, or phenolic resins.
  • the tackifying resin is compatible with the soft phase of the polyurethane, that is the part of the polyurethane molecule derived from the polybutadiene polyol.
  • Hydrogenated hydrocarbon resins or aliphatic oligomers are particularly preferred.
  • An example of a commercially available hydrogenated aliphatic oligomer resin is REGALITE R91 (REGALITE is a trademark), marketed by Hercules.
  • the tackifying resin if present, is typically used in amounts up to 400 parts by weight (pbw) per 100 parts of polyurethane, preferably in an amount of from 10 to 300 pbw, more preferably from 50 to 200 pbw.
  • any tackifying resin and any plasticizer other additives such as antioxidants, UV stabilisers, fillers; and flame retarders may be present, depending on the specific conditions under which the structural adhesive composition is to be used. It belongs to the skill of the skilled person in this field to select any appropriate additional additives and the desired amount to be added to the structural adhesive composition of this invention.
  • the present invention relates to a process for preparing a structural adhesive which comprises mixing, and reacting a mixture of a first and a second component, wherein the first component comprises a hydrogenated polybutadiene polyol having a functionality in the range of from 1.5 to 2.5 and a 1,2 vinyl content prior to hydrogenation of from 30 to 70% by weight and the second component comprises a polyisocyanate having a functionality in the range of from 2 to 3, or wherein the first component comprises a polymeric polyol, having a functionality in the range of from 1.5 to 2.5 and a number average molecular weight of 500 to 10,000, selected from the group consisting of a polyester polyol, polyether polyol, hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides, and the second component comprises an isocyanate-terminated prepolymer obtainable by reacting a hydrogenated polybutadiene polyol having a functionality in the range of from 1.5 to 2.5 and a 1,2 vinyl content prior to
  • the structural adhesive of the present invention may be used as a laminating adhesive, e.g. adhering a base polyolefin material and a covering material, e.g. a sheet, film or foam of polyvinyl choloride (PVC), polyamide or polyurethane.
  • a laminating adhesive e.g. adhering a base polyolefin material and a covering material, e.g. a sheet, film or foam of polyvinyl choloride (PVC), polyamide or polyurethane.
  • a structural adhesive composition was prepared by mixing CARADATE 30, a polymeric MDI having an isocyanate functionality of 2.7, (CARADATE is a trademark) and KRATON Liquid polymer L-2203 hydrogenated polybutadiene diol, having a functionality of 1.92, a 1,2 vinyl content prior to hydrogenation of 54% by weight, and a hydroxyl equivalent weight of 1720 (KRATON is a trademark and KRATON Liquid Polymer is available from Shell Chemical Companies).
  • the mixture had a [NCO)/[OH) ratio of 1.1.
  • the mixture (a warm melt) was used to glue a variety of substrates together and the mixture (structural adhesive) was (moisture) cured at 60°C for one hour to form a (cured) structural adhesive bond.
  • the glued section covered 8 cm 2 and had a thickness of approximately 200 ⁇ m.
  • Adhesive properties were determined by the lap shear test (ASTM 106). The lap shear test results are set, out in Table 1.
  • the structural adhesive of the present invention are capable of forming very strong adhesive bonds between a variety of substrates, including polyolefins.

Claims (13)

  1. Strukturklebstoffzusammensetzung, umfassend ein Polyurethan, das durch Umsetzen eines Polyisocyanats mit einer Funktionalität im Bereich von 2,1 bis 2,9 mit einem hydrierten Polybutadienpolyol erhältlich ist, das eine Funktionalität im Bereich von 1,5 bis 2,5 und einen 1,2-Vinylgehalt vor der Hydrierung von 30 bis 70 Gew.-% aufweist, wobei das NCO:OH-Molverhältnis im Bereich von größer als 1,05 bis zu 1,6 liegt.
  2. Strukturklebstoff nach Anspruch 1, worin die Funktionalität des Polyols von 1,7 bis 2,4 beträgt.
  3. Strukturklebstoff nach Anspruch 1 oder 2, worin die Funktionalität des Polyisocyanats von 2,5 bis 2,9 beträgt.
  4. Strukturklebstoff nach einem der vorstehenden Ansprüche, worin das hydrierte Polybutadienpolyol ein hydrierte Polybutadiendiol ist.
  5. Strukturklebstoff nach Anspruch 5, worin das Polybutadiendiol ein zahlenmittleres Molekulargewicht im Bereich von 500 bis 20.000 aufweist.
  6. Strukturklebstoff nach einem der vorstehenden Ansprüche, worin das Polyisocyanat ein polymeres MDI oder ein hydriertes polymeres MDI ist.
  7. Strukturklebstoff nach einem der vorstehenden Ansprüche, worin der Polyurethanteil des Polybutadienpolyols durch ein polymeres Polyol mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem zahlenmittleren Molekulargewicht von 500 bis 10.000 ersetzt worden ist, ausgewählt aus der aus Polyesterpolyol, Polyetherpolyol, Hydroxy-terminierten Polycarbonaten und Hydroxy-terminierten Copolymeren von Dialkylsiloxan und Alkylenoxiden bestehenden Gruppe.
  8. Strukturklebstoff nach einem der vorstehenden Ansprüche, der zusätzlich eine oder mehrere Komponenten umfaßt, ausgewählt unter einem Katalysator, einem klebrigmachenden Harz, einem Weichmacher, Antioxidationsmittel und Füllstoff.
  9. Mehrkomponentensystem zur Herstellung von Strukturklebstoffen, wie in einem der Ansprüche 1 bis 7 beansprucht, umfassend:
    (i) eine erste Komponente, umfassend ein hydriertes Polybutadienpolyol mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem 1,2-Vinylgehalt vor der Hydrierung von 30 bis 70 Gew.-%, und
    (ii) eine zweite Komponente, umfassend ein Polyisocyanat mit einer Funktionalität im Bereich von 2,1 bis 2,9, wobei die erste und die zweite Komponente in solchen Mengen vorliegen, daß das NCO:OH-Molverhältnis im Bereich von größer als 1,05 bis zu 1,6 liegt.
  10. Mehrkomponentensystem nach Anspruch 10, worin die erste und die zweite Komponente ein Lösungsmittel umfassen.
  11. Mehrkomponentensystem zur Herstellung von Strukturklebstoffen, wie in Anspruch 8 beansprucht, umfassend:
    (i) eine erste Komponente, umfassend ein polymeres Polyol mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem zahlenmittleren Molekulargewicht von 500 bis 10.000, ausgewählt aus der aus Polyesterpolyol, Polyetherpolyol, Hydroxy-terminierten Copolymeren von Dialkylsiloxan und Alkylenoxiden bestehenden Gruppe,
    (ii) ein zweite Komponente, umfassend ein Isocyanat-terminiertes Präpolymer, erhältlich durch Umsetzen eines hydrierten Polybutadienpolyols mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem 1,2-Vinylgehalt vor dem Hydrieren von 30 bis 70 Gew.-%, mit einem Überschuß an einem Polyisocyanat mit einer Funktionalität im Bereich von 2,1 bis 2,9,
    wobei die erste und die zweite Komponente in solchen Mengen vorliegen, daß das NCO:OH-Molverhältnis im Bereich von größer als 1,05 bis 1,6 liegt.
  12. Verfahren zur Herstellung eines Strukturklebstoffes, das ein Mischen und Reagieren eines Gemisches aus einer ersten und einer zweiten Komponente umfaßt, wobei die erste Komponente ein hydriertes Polybutadienpolyol mit einer Funktionalität im Bereich von 1,5 bis 2,5 umfaßt und die zweite Komponente ein Polyisocyanat mit einer Funktionalität im Bereich von 2,1 bis 2,9 umfaßt, oder worin die erste Komponente ein polymeres Polyol mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem zahlenmittleren Molekulargewicht von 500 bis 10.000, ausgewählt aus der aus Polyesterpolyol, Polyetherpolyol, Hydroxy-terminierten Copolymeren von Dialkylsiloxan und Alkylenoxiden bestehenden Gruppe, umfaßt und die zweite Komponente ein Isocyanat-terminiertes Präpolymer umfaßt, erhältlich durch Umsetzen eines hydrierten Polybutadienpolyols mit einer Funktionalität im Bereich von 1,5 bis 2,5 und einem 1,2-Vinylgehalt vor dem Hydrieren von 30 bis 70 Gew.-% mit einem Überschuß an einem Polyisocyanat mit einer Funktionalität im Bereich von 2,1 bis 2,9, wobei in dem Gemisch die erste und die zweite Komponente in solchen Mengen vorliegen, daß das NCO:OH-Molverhältnis im Bereich von größer als 1,05 bis 1,6 liegt.
  13. Gegenstände, die die Strukturklebstoffe, wie in einem der Ansprüche 1 bis 9 beansprucht, enthalten.
EP98946442A 1997-08-26 1998-08-25 Struktur-klebstoffe auf polyurethan basis Expired - Lifetime EP1012199B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98946442A EP1012199B1 (de) 1997-08-26 1998-08-25 Struktur-klebstoffe auf polyurethan basis

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97306483 1997-08-26
EP97306483 1997-08-26
PCT/EP1998/005477 WO1999010401A1 (en) 1997-08-26 1998-08-25 Structural polyurethane adhesives
EP98946442A EP1012199B1 (de) 1997-08-26 1998-08-25 Struktur-klebstoffe auf polyurethan basis

Publications (2)

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EP1012199A1 EP1012199A1 (de) 2000-06-28
EP1012199B1 true EP1012199B1 (de) 2002-05-08

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US (1) US6077925A (de)
EP (1) EP1012199B1 (de)
JP (1) JP2001514277A (de)
DE (1) DE69805310T2 (de)
ES (1) ES2173621T3 (de)
TW (1) TW446741B (de)
WO (1) WO1999010401A1 (de)
ZA (1) ZA987631B (de)

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US20060276613A1 (en) * 2005-05-12 2006-12-07 Iskender Yilgor Polyurethaneurea segmented copolymers
US7875149B2 (en) * 2005-06-08 2011-01-25 Ppg Industries Ohio, Inc. Aircraft adhesive
EP1736491B1 (de) * 2005-06-20 2011-12-21 Huntsman International Llc Lignozelluloseverbundwerkstoffe, die eine verbesserte Hitzebeständigkeit aufweisen, Klebstoffsysteme und Verfahren
US9579869B2 (en) * 2009-02-17 2017-02-28 Henkel IP & Holding GmbH Liquid moisture curable polyurethane adhesives for lamination and assembly
KR20140085981A (ko) * 2012-12-28 2014-07-08 현대자동차주식회사 폴리우레탄과 가황고무 접합용 접착제
ES2955466T3 (es) * 2015-02-03 2023-12-01 Henkel Ag & Co Kgaa Adhesivos de poliuretano para la unión de películas de baja energía superficial
US10870952B2 (en) 2016-03-18 2020-12-22 Advanced Polymer Technologies Corp. Using a polyol mixture comprising PBD for creating a PU-based artificial turf
MA41766B1 (fr) * 2016-03-18 2018-10-31 Advanced Polymer Tech Corp Utilisation d'un mélange de polyols comprenant du pbd pour créer un gazon artificiel à base de pu
CA3010557A1 (en) * 2016-03-18 2017-09-21 Advanced Polymer Technology Corp. Using a polyol mixture comprising pbd for creating a pu-based artificial turf
KR101902180B1 (ko) * 2016-08-11 2018-09-28 삼화페인트공업주식회사 우레탄 수지 및 자기점착성이 우수한 수지 조성물
CN110283292A (zh) * 2019-06-11 2019-09-27 上海天洋热熔粘接材料股份有限公司 一种湿固化聚氨酯热熔胶及其制备方法
WO2021086541A1 (en) 2019-10-28 2021-05-06 Dow Global Technologies Llc Polyolefin-based laminating adhesive composition and recyclable laminate

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JPH0699677B2 (ja) * 1990-01-08 1994-12-07 サンスター技研株式会社 ポリウレタン系接着剤
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Publication number Publication date
ES2173621T3 (es) 2002-10-16
WO1999010401A1 (en) 1999-03-04
EP1012199A1 (de) 2000-06-28
TW446741B (en) 2001-07-21
US6077925A (en) 2000-06-20
DE69805310T2 (de) 2002-11-07
JP2001514277A (ja) 2001-09-11
ZA987631B (en) 1999-02-24
DE69805310D1 (de) 2002-06-13

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